JP2000204284A - Active energy ray-curing composition and film-forming process thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an active energy ray-curing composition which forms a film having a high curability, surface hardness, adhesion and solvent resistance. SOLUTION: The composition contains as essential components [A] a photosensitizer of the formula (wherein R1 and R2 are each an 1-8C alkyl group; and multiple R3 are identical to or different from each other and are each hydrogen atom or a 1-4C alkyl group), [B] at least one cationic photopolymerization initiator chosen from an iodonium salt, a sulfonium salt and a phosphonium salt and [C] a cationic photopolymerizable compound, wherein the blending ratio of the above-mentioned components [A], [B] and [C] is from 0.01 to 5 pts.wt. component [A] and from 0.1 to 20 pts.wt. component [B] against 100 pts.wt. component [C].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel active energy ray-curable composition and a method for forming a film thereof, and more particularly to an active energy comprising a photosensitizer, a cationic photopolymerization initiator and a cationic photopolymerizable compound. The present invention relates to a method for forming a coating film in which a radiation-curable composition is applied to the surface of a substrate and cured by irradiation with an active energy ray.

[0002]

2. Description of the Related Art Conventionally, an active energy ray-curable composition which is cured by an active energy ray such as an ultraviolet ray or an electron beam,
For example, it is widely used for applications such as paints, inks and adhesives.

As compounds which initiate cationic polymerization of epoxy or the like upon irradiation with active energy rays, there are onium salts represented by aromatic diazonium salts, iodonium salts, sulfonium salts, etc., phosphonium salts and metal attone complexes.

[0004] Since the active energy ray-curable composition can be cured in seconds and does not require heating, it enables high-speed curing and drying that could not be achieved with a thermosetting paint or a lacquer type, and is widely used in applications suitable for this. It's being used. Also,
Usually, since heating is not required, this is an energy saving type coating drying method. For this purpose, it is extremely important to obtain a cured film that is fast and has a good finish with less energy. For this purpose, it is extremely important to use a photosensitizer to effectively utilize active energy rays. Many photosensitizers have been described so far, for example, JP-A-3-237106, JP-A-10-15
07, USP 4,571,377, USP 5,085,
972, Organic materials for imaging (Bunshin Publishing, 19
July 8, 1993) p. 32-P. 143, p. 170 and the like.

[0005] However, there is a problem that the above-mentioned known composition is insufficient in curability and crosslinking property at high speed, and that the enamel type containing a pigment has insufficient curability.

[0006]

SUMMARY OF THE INVENTION The object of the present invention is to develop an active energy ray-curable composition which forms a film having excellent curability, surface hardness, adhesion and solvent resistance. is there.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, a composition obtained by blending a specific photosensitizer with a cationic photopolymerizable composition has been obtained. ,
The present inventors have found that a film having extremely good reactivity and good hardness and adhesion is formed, and the present invention has been completed.

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Photosensitizer used in the composition of the present invention
[A] is a compound represented by the above general formula (1). The C ₁ -C ₈ alkyl group of R ₁ and R ₂ represented by the general formula (1) may be linear or branched. Examples of the alkyl group include methyl, ethyl, n-propyl,
iso-propyl, n-butyl, iso-butyl, te
Examples include groups such as rt-butyl, pentyl, hexyl, heptyl, octyl and the like. Further, the C ₁ -C ₄ alkyl group for R ₃ may be linear or branched. Examples of the alkyl group include methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl and the like.

As the photosensitizer [A], for example, 9,10
Dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene,
10-dibutoxyanthracene, 9,10-dihexanoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 2-ethyl-9,10-dipropoxyanthracene 2-ethyl-9,10-dibutoxyanthracene, 2-methyl-9,10-dimethoxyanthracene,
2-methyl-9,10-diethoxyanthracene, 2-
Examples thereof include methyl-9,10-dipropoxyanthracene, 2-methyl-9,10-dibutoxyanthracene, 2-propyl-9,10-dimethoxyanthracene, and 2-propyl-9,10-diethoxyanthracene.

As the cationic photopolymerization initiator used in the present invention, an onium salt obtained by forming a counter ion with an anion of an iodonium cation, a sulfonium cation, or a phosphonium cation is used. These can be used alone or in combination of two or more.

As the iodonium cation, for example, the following general formula (2)

[0012]

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As the sulfonium cation, for example, the following general formula (3)

[0014]

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As the phosphonium cation, for example, the following general formula (4)

[0016]

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[0017]

In the above general formulas (2) to (4), R
_{4 to} R ₇ represent the following meanings.

R ₄ , R ₆ and R ₇ may be the same or different in the same general formula.

R ₄ is a C ₁ -C ₁₈ linear or branched chain which may be substituted by fluorine, chlorine, bromine, hydroxyl, carboxyl, mercapto, cyano, nitro or azide; A cyclic alkyl group or the following R ₇ (fluorine,
Chlorine, bromine, hydroxyl, carboxyl, mercapto,
Cyano group, a nitro group, a monocyclic good C ₆ -C ₁₈ optionally substituted with an azido group, either) fused polycyclic aryl group.

The C ₁ -C ₁₈ linear, branched or cyclic alkyl group which may be substituted by the fluorine, chlorine, bromine, hydroxyl, carboxyl, mercapto, cyano, nitro or azide group As methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl, octadecyl, isopropyl, isobutyl, sec-butyl, t-butyl, cyclopentyl Group, cyclohexyl group, 4-decylcyclohexyl group, fluoromethyl group, chloromethyl group, bromomethyl group, trifluoromethyl group, trichloromethyl group, tribromomethyl group, hydroxymethyl group, carboxymethyl group, mercaptomethyl group, cyanomethyl group Nitromethyl group, azidomethyl group and the like.

R5 represents a benzyl group, a substituted benzyl group, a phenacyl group, a substituted phenacyl group, a substituted allyl group, an alkoxyl group, a substituted alkoxyl group, an allylalkoxyl group, an aryloxy group, Shows a group selected from aryloxy groups.

The substituted benzyl group includes fluorine, chlorine, bromine, cyano, nitro, trifluoromethyl, hydroxyl, mercapto, methylsulfinyl, methylsulfonyl, acetyl, benzoyl, C _1-
C ₁₈ linear, branched or cyclic alkyl group, C ₁ -C ₁₈
Linear, branched or cyclic alkoxyl group of C ₂ -C ₁₈
And a benzyl group substituted with a group selected from the group consisting of linear, branched and cyclic alkoxycarbonyl groups. Further, the benzene ring in the benzyl group may have a C ₁₀ -C ₂₂ Examples of the structure include a structure that may form a condensed polycyclic aromatic ring.

Specific examples of these substituted benzyl groups include o-fluorobenzyl, m-fluorobenzyl, p-fluorobenzyl, o-chlorobenzyl,
m-chlorobenzyl group, p-chlorobenzyl group, o-bromobenzyl group, m-bromobenzyl group, p-bromobenzyl group, o-cyanobenzyl group, m-cyanobenzyl group, p-cyanobenzyl group, o- Nitrobenzyl group, m
-Nitrobenzyl group, p-nitrobenzyl group, 2,4-
Difluorophenylmethyl group, 2,6-dichlorophenylmethyl group, 2,4,6-tribromophenylmethyl group, pentafluorophenylmethyl group, p- (trifluoromethyl) benzyl group, 3,5-bis (trifluoromethyl ) Phenylmethyl group, o-hydroxybenzyl group, m-hydroxybenzyl group, p-hydroxybenzyl group, o-mercaptobenzyl group, m-mercaptobenzyl group, p-mercaptobenzyl group, o-methylsulfinylbenzyl group, m- Methylsulfinylbenzyl group, p-methylsulfinylbenzyl group, o-methylsulfonylbenzyl group, m-methylsulfonylbenzyl group, p-methylsulfonylbenzyl group, o-acetylbenzyl group, m-acetylbenzyl group, p-acetylbenzyl group , O-benzoylbe Jill group, m- benzoyl benzyl, p- benzoyl benzyl, o- methylbenzyl group, m- methylbenzyl group, p- methylbenzyl group, p- ethylbenzyl group, p- propyl benzyl group,
p-isopropylbenzyl group, pt-butylbenzyl group, p-octadecylbenzyl group, p-cyclohexylbenzyl group, o-methoxybenzyl group, m-methoxybenzyl group, p-methoxybenzyl group, p-ethoxybenzyl group, p-propoxybenzyl group, p-isopropoxybenzyl group, pt-butoxybenzyl group, p-octadecylbenzyl group, p-cyclohexaneoxybenzyl group, o-methoxycarbonylbenzyl group, m-methoxycarbonylbenzyl group, p- Methoxycarbonylbenzyl group, p-ethoxycarbonylbenzyl group, p-propoxycarbonylbenzyl group, p-isopropoxycarbonylbenzyl group, pt-butoxycarbonylbenzyl group, p-octadecyloxycarbonylbenzyl group,
p-cyclohexaneoxycarbonylbenzyl group, 1-
Examples include a naphthylmethyl group, a 2-naphthylmethyl group, a 9-anthrylmethyl group, a 1-pyrenylmethyl group, a 5-naphthacenylmethyl group, and a 6-pentacenylmethyl group.

The substituted phenacyl group includes fluorine, chlorine, bromine, cyano, nitro, trifluoromethyl, hydroxyl, mercapto, methylsulfinyl, methylsulfonyl, acetyl, benzoyl, C ₁ -C
C ₁₈ linear, branched or cyclic alkyl group, C ₁ -C ₁₈
Linear, branched or cyclic alkoxyl group of C ₂ -C ₁₈
And a phenacyl group substituted by a group selected from the group consisting of linear, branched and cyclic alkoxycarbonyl groups. Further, the benzene ring in the phenacyl group is condensed by C _{10 to} C ₂₂ with an unsaturated hydrocarbon group. Examples of the structure include a structure that may form a polycyclic aromatic ring.

Specific examples of these substituted phenacyl groups include o-fluorophenacyl, m-fluorophenacyl, p-fluorophenacyl, o-chlorophenacyl, m-chlorophenacyl, p-chlorophenacyl group, o-bromophenacyl group, m-bromophenacyl group, p-bromophenacyl group, o-cyanophenacyl group, m-cyanophenacyl group, p-cyanophenacyl group, o-nitrophenacyl group, m-nitrophenacyl group P-nitrophenacyl group, 2,4-difluorophenylcarbonylmethyl group, 2,6-dichlorophenylcarbonylmethyl group, 2,4,6-tribromophenylcarbonylmethyl group, pentafluorophenylcarbonylmethyl group, p- ( Trifluoromethyl) phenacyl group,
3,5-bis (trifluoromethyl) phenylcarbonylmethyl group, o-hydroxyphenacyl group, m-hydroxyphenacyl group, p-hydroxyphenacyl group, o-
Mercaptophenacyl group, m-mercaptophenacyl group, p-mercaptophenacyl group, o-methylsulfinylphenacyl group, m-methylsulfinylphenacyl group, p-methylsulfinylphenacyl group, o-methylsulfonylphenacyl group M-methylsulfonylphenacyl group, p-methylsulfonylphenacyl group, o-acetylphenacyl group, m-acetylphenacyl group, p-acetylphenacyl group, o-benzoylphenacyl group, m
-Benzoylphenacyl group, p-benzoylphenacyl group, o-methylphenacyl group, m-methylphenacyl group, p-methylphenacyl group, p-ethylphenacyl group, p-propylphenacyl group, p- Isopropylphenacyl group, pt-butylphenacyl group, p-octadecylphenacyl group, p-cyclohexylphenacyl group,
o-methoxyphenacyl group, m-methoxyphenacyl group, p-methoxyphenacyl group, p-ethoxyphenacyl group, p-propoxyphenacyl group, p-isopropoxyphenacyl group, pt-butoxyphenacyl Group, p-
Octadecyloxyphenacyl group, p-cyclohexaneoxyphenacyl group, o-methoxycarbonylphenacyl group, m-methoxycarbonylphenacyl group, p-methoxycarbonylphenacyl group, p-ethoxycarbonylphenacyl group, p-propoxycarbonyl Phenacyl group, p-isopropoxycarbonylphenacyl group, p-
t-butoxycarbonylphenacyl group, p-octadecyloxycarbonylphenacyl group, p-cyclohexaneoxycarbonylphenacyl group, 1-naphthoylmethyl group, 2-naphthoylmethyl group, 9-anthroylmethyl group, 1-pyre And a carbonylcarbonylmethyl group, a 5-naphthacenylcarbonylmethyl group and a 6-pentacenylcarbonylmethyl group.

The substituted allyl group includes fluorine, nitro group, trifluoromethyl group, cyano group, acetyl group, benzoyl group, C ₁ -C ₁₈ linear, branched, cyclic alkyl, C ₂ -C ₁₈ linear, branched, cyclic alkoxycarbonyl group, an allyl group substituted by a group selected from a phenyl group.

Specific examples of these substituted allyl groups include a 2,3,3-trifluoro-2-propenyl group,
3,3-dinitro-2-propenyl group, 3,3-bis (trifluoromethyl) -2-propenyl group, 3,3-
Dicyano-2-propenyl group, 2-methyl-3,3-dicyano-2-propenyl group, 3-hexyl-3,3-dicyano-2-propenyl group, 2-octadecyl-3,3
-Dicyano-2-propenyl group, 2-isopropyl-
3,3-dicyano-2-propenyl group, 2-t-butyl-3,3-dicyano-2-propenyl group, 2-cyclohexyl-3,3-dicyano-2-propenyl group, 2-acetyl-3,3 -Dicyano-2-propenyl group, 2-benzoyl-3,3-dicyano-2-propenyl group, 2-
A phenyl-3,3-dicyano-2-propenyl group, 3,
3-bis (methoxycarbonyl) -2-propenyl group,
2-methyl-3,3-bis (methoxycarbonyl) -2
-Propenyl group, 2-hexyl-3,3-bis (methoxycarbonyl) -2-propenyl group, 2-octadecyl-3,3-bis (methoxycarbonyl) -2-propenyl group, 2-isopropyl-3,3- Bis (methoxycarbonyl) -2-propenyl group, 2-t-butyl-3,3
-Bis (methoxycarbonyl) -2-propenyl group, 2
-Cyclohexyl-3,3-bis (methoxycarbonyl) -2-propenyl group, 2-acetyl-3,3-bis (methoxycarbonyl) -2-propenyl group, 2-benzoyl-3,3-bis (methoxycarbonyl) group -2-propenyl group, 2-phenyl-3,3-bis (methoxycarbonyl) -2-propenyl group, 2-phenyl-3,3
-Bis (hexyloxycarbonyl) -2-propenyl group, 2-phenyl-3,3-bis (octadecyloxycarbonyl) -2-propenyl group, 2-phenyl-3,
Examples thereof include a 3-bis (t-butoxycarbonyl) -2-propenyl group and a 2-phenyl-3,3-bis (cyclohexyloxycarbonyl) -2-propenyl group.

Examples of the alkoxyl group include C ₁ -C ₁₈ linear, branched, and cyclic alkoxyl groups, and include methoxy, ethoxy, propoxy, butoxy, octyloxy, octadecoxy, and octadecaneoxy. Examples include a propoxy group, a t-butoxy group, a cyclopentyloxy group, and a cyclohexyloxy group.

The substituted alkoxyl group includes fluorine,
A C ₁ -C ₁₈ linear, branched or cyclic alkoxyl group substituted with a group selected from chlorine, bromine, cyano group, nitro group, trifluoromethyl group and hydroxyl group; -Chloroethoxy group, 3-bromopropoxy group, 4-cyanobutoxy group, 8-nitrooctyloxy group, 18-trifluoromethyloctadecaneoxy group, 2-hydroxyisopropoxy group, trichloromethoxy group and the like.

The aryloxy group is a C ₆ -C ₁₈ monocyclic or condensed polycyclic aryloxy group, and is a phenoxy group,
1-naphthyloxy group, 2-naphthyloxy group, 9-anthryloxy group, 9-phenanthryloxy group, 1-
Pyrenyloxy group, 5-naphthacenyloxy group, 1-indenyloxy group, 2-azulenyloxy group, 1-acenaphthyloxy group, 9-fluorenyloxy group, o-tolyloxy group, m-tolyloxy group, p- Tolyloxy group, 2,3-xylyloxy group, 3,5-xylyloxy group, mesityloxy group, p-cumenyloxy group, p-
Decylphenoxy, p-cyclohexylphenoxy, 4-phenylphenoxy and the like.

The substituted aryloxy group is a C ₆ -C ₁₈ monocyclic ring substituted by a group selected from fluorine, chlorine, bromine, hydroxyl, carboxyl, mercapto, cyano, nitro and azide. A condensed polycyclic aryloxy group, o-fluorophenoxy group, m-chlorophenoxy group, p-bromophenoxy group, p-hydroxyphenoxy group, m-carboxyphenoxy group, o-mercaptophenoxy group, p-cyanophenoxy group Group, m-nitrophenoxy group, m-azidophenoxy group, 2-chloro-
Examples thereof include a 1-naphthyloxy group, a 10-cyano-9-anthryloxy group, and an 11-nitro-5-naphthacenyloxy group.

[0033] In these R ₅ 5, preferred are fluorine, a cyano group, a nitro group, a trifluoromethyl group, C1 -C4 linear, branched acyl group, C ₂ ~
C ₅ straight-chain, branched-chain alkoxycarbonyl group, a benzoyl group, methylsulfinyl group, methylsulfonyl group, p- tosyl group such electron-withdrawing substituted benzyl group with a group, phenacyl group, allyl group. Such specific examples include an o-cyanobenzyl group, a p-cyanobenzyl group, an o-nitrobenzyl group, a p-nitrobenzyl group, a pentafluorophenylmethyl group, a 3,5-
Bis (trifluoromethyl) phenylmethyl group, o-acetylbenzyl group, p-acetylbenzyl group, o-methoxycarbonylbenzyl group, p-methoxycarbonylbenzyl group, ot-butoxycarbonylbenzyl group, p
-T-butoxycarbonylbenzyl group, o-benzoylbenzyl group, p-benzoylbenzyl group, o-methylsulfinylbenzyl group, p-methylsulfinylbenzyl group, o-methylsulfonylbenzyl group, p-methylsulfonylbenzyl group, o- A (p-tosyl) benzyl group,
o-cyanophenacyl group, p-cyanophenacyl group, o
-Nitrophenacyl group, p-nitrophenacyl group, pentafluorobenzoylmethyl group, 3,5-bis (trifluoromethyl) benzoylmethyl group, o-acetylphenacyl group, p-acetylphenacyl group, o-methoxy Carbonylphenacyl group, p-methoxycarbonylphenacyl group, ot-butoxycarbonylphenacyl group, p
-T-butoxycarbonylphenacyl group, o-benzoylphenacyl group, p-benzoylphenacyl group, o-methylsulfinylphenacyl group, p-methylsulfinylphenacyl group, o-methylsulfonylphenacyl group,
p-methylsulfonylphenacyl group, o- (p-tosyl) phenacyl group, p- (p-tosyl) phenacyl group,
3,3-dicyano-2-propenyl group, 1-methyl-
3,3-dicyano-2-propenyl group, 2-phenyl-
3,3-dicyano-2-propenyl group, 3,3-bis (methoxycarbonyl) -2-propenyl group, 2-phenyl-3,3-bis (methoxycarbonyl) -2-propenyl group, cyanomethoxy group, acetyl Examples include a methoxy group, a benzoylmethoxy group, a p-cyanophenoxy group, and a pentafluorophenylmethoxy group.

R ₆ is a C ₁ -C ₁₈ linear or branched chain which may be substituted by fluorine, chlorine, bromine, hydroxyl, carboxyl, mercapto, cyano, nitro or azide; A cyclic alkyl group, or a C _1- which may be substituted by fluorine, chlorine, bromine, hydroxyl, carboxyl, mercapto, cyano, nitro or azide;
It represents any of a _C18 linear alkoxy group, a branched alkoxy group, and a cyclic alkoxy group.

The C ₁ -C ₁₈ linear, branched or cyclic alkyl group which may be substituted by the fluorine, chlorine, bromine, hydroxyl, carboxyl, mercapto, cyano, nitro or azide group. represent the same meanings as described in R _4.

The C ₁ -C ₁₈ linear, branched, or cyclic alkoxy group which may be substituted by the fluorine, chlorine, bromine, hydroxyl, carboxyl, mercapto, cyano, nitro or azide group As a methoxy group, ethoxy group, propoxy group, butoxy group, octyloxy group, octadecaneoxy group, isopropoxy group, t-butoxy group, cyclopentyloxy group, cyclohexyloxy group, trifluoromethoxy group, chloromethoxy group, bromo Examples include methoxy group, trifluoromethoxy group, trichloromethoxy group, tribromomethoxy group, hydroxymethoxy group, carboxymethoxy group, mercaptomethoxy group, cyanomethoxy group, nitromethoxy group, and azidomethoxy group.

R ₇ is a C ₆ -C ₁₈ monocyclic or condensed polycyclic aryl group which may be substituted by fluorine, chlorine, bromine, hydroxyl, carboxyl, mercapto, cyano, nitro or azide. Is shown. Specifically, a phenyl group, 1-
Naphthyl group, 2-naphthyl group, 9-anthryl group, 9-
Phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azulenyl group, 1-acenaphthyl group, 9-fluorenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2, 3-xylyl group, 2,5-
Xylyl group, mesityl group, p-cumenyl group, p-dodecylphenyl group, p-cyclohexylphenyl group, 4-biphenyl group, o-fluorophenyl group, m-chlorophenyl group, p-bromophenyl group, p-hydroxyphenyl group , M-carboxyphenyl group, o-mercaptophenyl group, p-cyanophenyl group, m-nitrophenyl group, m-azidophenyl group and the like.

Z represents an oxygen or sulfur atom.

Examples of the sulfonium cation include the following.

Benzyl sulfonium cation: dimethyl (benzyl) sulfonium, dimethyl (o-fluorobenzyl) sulfonium, dimethyl (m-chlorobenzyl) sulfonium, dimethyl (p-bromobenzyl) sulfonium, dimethyl (p-cyanobenzyl) sulfonium, dimethyl (M-nitrobenzyl) sulfonium,
Dimethyl (2,4,6-tribromophenylmethyl) sulfonium, dimethyl (pentafluorophenylmethyl) sulfonium, dimethyl (p- (trifluoromethyl) benzyl) sulfonium, dimethyl (p-hydroxybenzyl) sulfonium, dimethyl (p- Mercaptobenzyl) sulfonium, dimethyl (p-methylsulfinylbenzyl) sulfonium, dimethyl (p-methylsulfonylbenzyl) sulfonium, dimethyl (o-acetylbenzyl) sulfonium, dimethyl (o-benzoylbenzyl) sulfonium, dimethyl (p-methylbenzyl) Sulfonium, dimethyl (p-isopropylbenzyl) sulfonium, dimethyl (p-octadecylbenzyl) sulfonium, dimethyl (p-cyclohexylbenzyl) sulfonium Arm, dimethyl (p- methoxybenzyl) sulfonium, dimethyl (o-methoxycarbonyl benzyl) sulfonium, dimethyl (p- isopropoxycarbonyl benzyl) sulfonium, dimethyl (2
-Naphthylmethyl) sulfonium, dimethyl (9-anthrylmethyl) sulfonium, diethyl (benzyl) sulfonium, methylethyl (benzyl) sulfonium,
Methylphenyl (benzyl) sulfonium, diphenyl (benzyl) sulfonium, diisopropyl (benzyl) sulfonium and the like.

Phenacylsulfonium cations: dimethyl (phenacyl) sulfonium, dimethyl (o-fluorophenacyl) sulfonium, dimethyl (m-chlorophenacyl) sulfonium, dimethyl (p-bromophenacyl) sulfonium, dimethyl (p-cyanophenacyl) sulfonium, Dimethyl (m-nitrophenacyl)
Sulfonium, dimethyl (2,4,6-tribromophenylmethyl) sulfonium, dimethyl (p- (trifluoromethyl) phenacyl) sulfonium, dimethyl (p
-Hydroxyphenacyl) sulfonium, dimethyl (p
-Mercaptophenacyl) sulfonium, dimethyl (p
-Methylflufinylphenacyl) sulfonium, dimethyl (p-methylsulfonylphenacyl) sulfonium, dimethyl (o-acetylphenacyl) sulfonium, dimethyl (o-benzoylphenacyl) sulfonium, dimethyl (p-methylphenacyl) sulfonium,
Dimethyl (p-isopropylphenacyl) sulfonium, dimethyl (p-octadecylphenacyl) sulfonium, dimethyl (p-cyclohexylphenacyl) sulfonium, dimethyl (p-methoxyphenacyl) sulfonium, dimethyl (o-methoxycarbonylphenacyl) sulfonium Dimethyl (p-isopropoxycarbonylphenacyl) sulfonium, dimethyl (2-naphthoylmethyl) sulfonium, dimethyl (9-anthroylmethyl) sulfonium, diethyl (phenacyl) sulfonium, methylethyl (phenacyl) sulfonium, methylphenyl (phenacyl) ) Sulfonium, diphenyl (phenacyl) sulfonium, diisopropyl (phenacyl) sulfonium, tetramethylene (phenacyl) sulfonium, pen Methylene (phenacyl) sulfonium, hexamethylene (phenacyl) sulfonium, ethylenedioxy (phenacyl) sulfonium, diethylene dioxy (phenacyl) sulfonium, ethylene dithio (phenacyl) sulfonium.

Allylsulfonium cations: dimethyl (allyl) sulfonium, dimethyl (2,3,3-trifluoro-2-propenyl) sulfonium, dimethyl (3,3-dicyano-2-propenyl) sulfonium,
Dimethyl (2-methyl-3,3-dicyano-2-propenyl) sulfonium, dimethyl (2-acetyl-3,3
-Dicyano-2-propenyl) sulfonium, dimethyl (2-benzoyl-3,3-dicyano-2-propenyl) sulfonium, dimethyl (2-phenyl-3,3-
Dicyano-2-propenyl) sulfonium, dimethyl (3,3-bis (methoxycarbonyl) -2-propenyl) sulfonium and the like.

Alkoxysulfonium cations: dimethyl (methoxy) sulfonium, dimethyl (ethoxy) sulfonium, dimethyl (propoxy) sulfonium, dimethyl (butoxy) sulfonium, dimethyl (octyloxy) sulfonium, dimethyl (octadecaneoxy) sulfonium, dimethyl (isopropoxy) Sulfonium, dimethyl (t-butoxy) sulfonium, dimethyl (scopentyloxy) sulfonium, dimethyl (cyclohexyloxy) sulfonium, dimethyl (fluoromethoxy) sulfonium, dimethyl (2-chloroethoxy) sulfonium, dimethyl (3-bromopropoxy) sulfonium, Dimethyl (4-cyanobutoxy)
Sulfonium, dimethyl (8-nitrooctyloxy)
Sulfonium, dimethyl (18-trifluoromethyloctadecaneoxy) sulfonium, dimethyl (2-hydroxyisopropoxy) sulfonium, dimethyl (tris (trichloromethyl) methyl) sulfonium and the like.

Aryloxysulfonium cations: dimethyl (phenoxy) sulfonium, dimethyl (1-naphthyloxy) sulfonium, dimethyl (2-naphthyloxy) sulfonium, dimethyl (9-anthryloxy) sulfonium, dimethyl (9-phenanthryloxy) ) Sulfonium, dimethyl (p-tolyloxy) sulfonium, dimethyl (2,3-xylyloxy) sulfonium, dimethyl (o-fluorophenoxy) sulfonium, dimethyl (m-chlorophenoxy) sulfonium, dimethyl (p-bromophenoxy) sulfonium,
Dimethyl (p-hydroxyphenoxy) sulfonium,
Dimethyl (m-carboxyphenoxy) sulfonium, dimethyl (o-mercaptophenoxy) sulfonium, dimethyl (p-cyanophenoxy) sulfonium,
Dimethyl (m-nitrophenoxy) sulfonium, dimethyl (m-azidophenoxy) sulfonium, dimethyl (2-chloro-1-naphthyloxysulfonium, dimethyl (11-nitro-5-naphthacenyl) sulfonium and the like.

(Sulfoxonium cation) Benzyl sulfoxonium cation: dimethyl (benzyl) sulfoxonium, dimethyl (p-bromobenzyl) sulfoxonium, dimethyl (p-cyanobenzyl) sulfoxonium, dimethyl (m-nitro) Benzyl) sulfoxonium, dimethyl (pentafluorophenylmethyl) sulfoxonium, dimethyl (p-hydroxybenzyl) sulfoxonium, dimethyl (o-acetylbenzyl) sulfoxonium, dimethyl (o-benzoylbenzyl) sulfoxonium, Dimethyl (p-isopropylbenzyl) sulfoxonium, dimethyl (p
-Methoxybenzyl) sulfoxonium, dimethyl (o
-Methoxycarbonylbenzyl) sulfoxonium, dimethyl (2-naphthylmethyl) sulfoxonium, dimethyl (9-anthrylmethyl) sulfoxonium, diethyl (benzyl) sulfoxonium, methylethyl (benzyl) sulfoxonium, methyl Phenyl (benzyl) sulfoxonium, diphenyl (benzyl) sulfoxonium, diisopropyl (benzyl) sulfoxonium and the like.

Phenacylsulfoxonium cation: dimethyl (phenacyl) sulfoxonium, dimethyl (p
-Bromophenacyl) sulfoxonium, dimethyl (p
-Cyanophenacyl) sulfoxonium, dimethyl (m
-Nitrophenacyl) sulfoxonium, dimethyl (2,4,6-tribromophenylmethyl) sulfoxonium, dimethyl (p-hydroxyphenacyl) sulfoxonium, dimethyl (p-mercaptophenacyl) sulfoxonium, Dimethyl (o-benzoylphenacyl) sulfoxonium, dimethyl (p-methylphenacyl) sulfoxonium, dimethyl (p-methoxyphenacyl) sulfoxonium, dimethyl (o-methoxycarbonylphenacyl) sulfoxonium, dimethyl (2-
Naphthylmethyl) sulfoxonium, dimethyl (9-anthrylmethyl) sulfoxonium, diethyl (phenacyl) sulfoxonium, methylethyl (phenacyl)
Sulfoxonium, methylphenyl (phenacyl) sulfoxonium, diphenyl (phenacyl) sulfoxonium, diisopropyl (phenacyl) sulfoxonium, tetramethylene (phenacyl) sulfoxonium and the like.

Allylsulfoxonium cations: dimethyl (allyl) sulfoxonium, dimethyl (3,3-dicyano-2-propenyl) sulfoxonium, dimethyl (2-benzoyl-3,3-dicyano-2-propenyl) sulfo Xonium, dimethyl (2-phenyl-3,
3-dicyano-2-propenyl) sulfoxonium, dimethyl (3,3-bis (methoxycarbonyl) -2-propenyl) sulfoxonium and the like.

Alkoxysulfoxonium cations: dimethyl (ethoxy) sulfoxonium, dimethyl (propoxy) sulfoxonium, dimethyl (octyloxy) sulfoxonium, dimethyl (isopropoxy) sulfoxonium, dimethyl (cyclohexyloxy) sulfoxonium And dimethyl (2-chloroethoxy) sulfoxonium.

Aryloxysulfoxonium cations: dimethyl (phenoxy) sulfoxonium, dimethyl (2-naphthyloxy) sulfoxonium, dimethyl (9-anthryloxy) sulfoxonium, dimethyl (p-tolyloxy) sulfoxonium , Dimethyl (m
-Chlorophenoxy) sulfoxonium, dimethyl (m
-Carboxyphenoxy) sulfoxonium, dimethyl (p-cyanophenoxy) sulfoxonium and the like.

Triarylsulfonium cations: triphenylsulfonium, tris (p-tolyl) sulfonium, tris (phenyl) sulfonium, tris (2,
6-dimethylphenyl) sulfonium, tris (p-cyanophenyl) sulfonium, tris (p-chlorophenyl) sulfonium and the like.

Triarylsulfoxonium cation:
Triphenylsulfoxonium, tris (p-tolyl)
Sulfoxonium, tris (phenyl) sulfoxonium, tris (2,6-dimethylphenyl) sulfoxonium, tris (p-cyanophenyl) sulfoxonium, tris (p-chlorophenyl) sulfoxonium and the like.

Examples of the phosphonium cation include the following.

Benzylphosphonium cations: trimethylbenzylphosphonium, triethylbenzylphosphonium, triphenylbenzylphosphonium, triphenyl (p-fluorobenzyl) phosphonium, triphenyl (o-chlorobenzyl) phosphonium, triphenyl (m-bromobenzyl) phosphonium, Triphenyl (p-cyanobenzyl) phosphonium, triphenyl (m-nitrobenzyl) phosphonium, triphenyl (o-hydroxybenzyl) phosphonium, triphenyl (o-acetylbenzyl) phosphonium, triphenyl (m-benzoylbenzyl) phosphonium, Triphenyl (p-methylbenzyl) phosphonium, triphenyl (p-isopropoxybenzyl) phosphonium, triphenyl (o-methoxy) Rubonirubenjiru) phosphonium, triphenyl (1-naphthylmethyl) phosphonium, triphenyl (9-anthrylmethyl) phosphonium like.

Examples of phenacylphosphonium cations: trimethylphenacylphosphonium, triethylphenacylphosphonium, triphenylphenacylphosphonium, triphenyl (p-fluorophenacyl) phosphonium, triphenyl (o-chlorophenacyl) phosphonium, triphenyl (M-bromophenacyl) phosphonium, triphenyl (p-cyanophenacyl) phosphonium, triphenyl (m-nitrophenacyl) phosphonium, triphenyl (o-hydroxyphenacyl) phosphonium, triphenyl (o-acetylphenacyl) phosphonium, triphenyl Phenyl (m-benzoylphenacyl) phosphonium, triphenyl (p-methylphenacyl) phosphonium, triphenyl (p-isopropoxyphenacyl) phosphonium Arm, triphenyl (o-methoxycarbonyl phenacyl) phosphonium, triphenyl (1- naphthoquinone Ciro yl methyl) phosphonium, triphenyl (9 anthrocyclins yl methyl) phosphonium like.

Allylphosphonium cations: triphenylallylphosphonium, triphenyl (3,3-dicyano-2-propenyl) phosphonium, triphenyl (2
-Hexyl-3,3-dicyano-2-propenyl) phosphonium, triphenyl (2-acetyl-3,3-dicyano-2-propenyl) phosphonium, triphenyl (2-phenyl-3,3-dicyano-2-propenyl) )
Phosphonium and the like.

Alkoxyphosphonium cations: triphenylmethoxyphosphonium, triphenylbutoxyphosphonium, triphenyloctadecyloxyphosphonium, triphenylisopropoxyphosphonium, triphenyl (2-chloroethoxy) phosphonium, triphenyl (4-cyanobutoxy) phosphonium and the like.

Aryloxyphosphonium cations: triphenylphenoxyphosphonium, triphenyl (1
-Naphthyloxy) phosphonium, triphenyl (2-
Naphthyloxy) phosphonium, triphenyl (9-anthryloxy) phosphonium, triphenyl (p-tolyloxy) phosphonium, triphenyl (2,3-xylyloxy) phosphonium, triphenyl (p-hydroxyphenoxy) phosphonium, triphenyl (m −
(Carboxyphenoxy) phosphonium and the like.

Examples of the iodonium cation include the following.

Furyl or thienyl iodonium cations: difuryl iodonium, dithienyl iodonium, bis (4,5-dimethyl-2-furyl) iodonium, bis (5-chloro-2-thienyl) iodonium,
Bis (5-cyano-2-furyl) iodonium, bis (5-nitro-2-thienyl) iodonium, bis (5
-Acetyl-2-furyl) iodonium, bis (5-carboxy-2-thienyl) iodonium, bis (5-methoxycarbonyl-2-furyl) iodonium, bis (5-phenyl-2-furyl) iodonium, bis (5
-(P-methoxyphenyl) -2-thienyl) iodonium, bis (5-vinyl-2-furyl) iodonium,
Bis (5-ethynyl-2-thienyl) iodonium, bis (5-cyclohexyl-2-furyl) iodonium,
Bis (5-hydroxy-2-thienyl) iodonium,
Bis (5-phenoxy-2-furyl) iodonium, bis (5-mercapto-2-thienyl) iodonium, bis (5-butylthio-2-thienyl) iodonium, bis (5-phenylthio-2-thienyl) iodonium and the like.

Diaryliodonium cations: diphenyliodonium, bis (p-tolyl) iodonium,
Bis (p-octylphenyl) iodonium, bis (p
-Octadecylphenyl) iodonium, bis (p-octyloxyphenyl) iodonium, bis (p-octadecyloxyphenyl) iodonium, bis (p-octadecyloxyphenyl) iodonium and the like.

As the anion to be a counter ion of these cations, X- is, for example, a halogen anion such as a fluorine anion, a chloride anion, a bromine anion or an iodine anion, an acetate anion, a trifluoroacetate anion, a sulfate anion or a hydrogen sulfate. Anions, methanesulfate anions, trifluoromethanesulfate anions, perchlorate anions, tetrafluoroborate anions, hexafluorophosphate anions, hexachloroantimonate anions, hexafluoroantimonate anions, and the like.

The cationic photopolymerizable compound used in the present invention is a compound which is irradiated with light under a cationic photopolymerization initiator [B] and a photosensitizer [A] to be crosslinked or polymerized to have a high molecular weight by a polymerization reaction. It is. Specifically, for example, epoxy compounds, styrenes, vinyl compounds, vinyl ethers, spiroorthoesters, bicycloorthoesters, spiroorthocarbonates, cyclic ethers, lactones, oxazolines, aziridines, cyclosiloxanes , Ketals, cyclic acid anhydrides, lactams, alkoxysilane compounds, aryl dialdehydes and the like.

Examples of the epoxy compound include conventionally known aromatic epoxy compounds, alicyclic epoxy compounds, and aliphatic epoxy compounds.

Examples of the aromatic epoxy compound include a monofunctional epoxy compound such as phenylglycidyl ether and a polyglycidyl ether of a polyhydric phenol having at least one aromatic ring or an alkylene oxide adduct thereof. Glycidyl ethers produced by the reaction of bisphenol compounds such as bisphenol A, tetrabromobisphenol A, bisphenol F and bisphenol S or alkylene oxide (eg, ethylene oxide, propylene oxide, butylene oxide, etc.) adducts of bisphenol compounds with epichlorohydrin , Novolak epoxy resins (eg, phenol novolak epoxy resin, cresol novolak epoxy resin, brominated phenol novolak Epoxy resin, etc.), etc. trisphenolmethane triglycidyl ether.

Examples of the alicyclic epoxy compound include 4-vinylcyclohexene monoepoxide, norbornene monoepoxide, limonene monoepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, and bis- (3,4- Epoxycyclohexylmethyl) adipate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexanone-meta-dioxane, bis (2,3-epoxycyclopentyl) ether, 2-
(3,4-epoxycyclohexyl-5,5-spiro-
3,4-epoxy) cyclohexanone-meta-dioxane, 2,2-bis [4- (2,3-epoxypropoxy) cyclohexyl] hexafluoropropane, BHP
E-3150 (manufactured by Daicel Chemical Industries, Ltd., alicyclic epoxy resin (softening point: 71 ° C.)).

As the aliphatic epoxy compound, for example,
1,4-butanediol diglycidyl ether, 1,6
-Hexanediol diglycidyl ether, ethylene glycol diglycidyl ether, ethylene glycol monoglycidyl ether, propylene glycol diglycidyl ether, propylene glycol monoglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, Neopentyl glycol monoglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane diglycidyl ether,
Examples include trimethylolpropane monoglycidyl ether, trimethylolpropane triglycidyl ether, diglycerol triglycidyl ether, sorbitol tetraglycidyl ether, allyl glycidyl ether, and 2-ethylhexyl glycidyl ether.

Examples of the styrenes include styrene, α-methylstyrene, p-methylstyrene, p-chloromethylstyrene and the like. As the vinyl compound, N-
Vinyl carbazole, N-vinyl pyrrolidone and the like.

As vinyl ethers, for example, n-
(Or iso-, t-) butyl vinyl ether, cyclohexyl vinyl ether, hydroxybutyl vinyl ether, 1,4-butanediol divinyl ether, ethylene glycol divinyl ether, ethylene glycol monovinyl ether, triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, Propylene glycol divinyl ether, propylene glycol monovinyl ether, neopentyl glycol divinyl glycol, neopentyl glycol monovinyl glycol, glycerol divinyl ether, glycerol trivinyl ether, trimethylol propane monovinyl ether, trimethylol propane divinyl ether, trimethylol propane trivinyl ether, diglycerol Trivinyl ether, sorbitol tetravinyl ether, cyclohexane dimethanol divinyl ether, hydroxybutyl vinyl ether, dodecyl vinyl ether, 2,2-bis (4-cyclohexanol) propane divinyl ether, 2,2-bis (4-cyclohexanol) trifluoropropanedi Alkyl vinyl ethers such as vinyl ether; alkenyl vinyl ethers such as allyl vinyl ether; alkynyl vinyl ethers such as ethynyl vinyl ether and 1-methyl-2-propenyl vinyl ether;
Vinyl ether styrene, hydroquinone divinyl ether, phenyl vinyl ether, p-methoxyphenyl vinyl ether, bisphenol A divinyl ether,
Aryl vinyl ethers such as tetrabromobisphenol A divinyl ether, bisphenol F divinyl ether, phenoxyethylene vinyl ether, p-bromophenoxyethylene vinyl ether, 1,4-benzenedimethanol divinyl ether, Nm-chlorophenyldiethanolamine divinyl ether, m-phenylene Examples include aralkyl divinyl ethers such as bis (ethylene glycol) divinyl ether, urethane polyvinyl ether (for example, VECtomer 2010, manufactured by ALLIED-SIGNAL) and the like.

The spiro orthoesters include 1,1
4,6-trioxaspiro (4,4) nonane, 2-methyl-1,4,6-trioxaspiro (4,4) nonane,
1,4,6-trioxaspiro (4,5) decane and the like, as bicycloorthoesters, 1-phenyl-4-ethyl-2,6,7-trioxabicyclo (2,5
2,2) octane, 1-ethyl-4-hydroxymethyl-2,6,7-trioxabicyclo (2,2,2) octane and the like include spiroorthocarbonates,
Cyclic ethers such as 1,5,7,11-tetraoxaspiro (5,5) undecane, 3,9-dibenzyl-1,5,7,11-tetraoxaspiro (5,5) undecane; Can be

Examples of the cyclic ethers include oxetanes such as oxetane and phenyloxetane; tetrahydrofurans such as tetrahydrofuran and 2-methyltetrahydrofuran; tetrahydrosilanes such as tetrahydrosilane and 3-propyltetrahydrosilane; trimethylene oxide; and s-trioxane. And so on. Lactones include β-propiolactone, γ-
Butyl lactone, δ-caprolactone, δ-valerolactone and the like can be mentioned. Examples of the oxazolines include oxazoline, 2-phenyloxazoline, 2-decyloxazoline and the like.

As the aziridine, aziridine, N-
Ethyl aziridine and the like. Examples of cyclosiloxanes include hexamethyltrisiloxane, octamethylcyclotetrasiloxane, triphenyltrimethylcyclotrisiloxane, and the like. Ketals include 1,3-dioxolan, 1,3-dioxane,
2,2-dimethyl-1,3-dioxane, 2-phenyl-1,3-dioxane, 2,2-dioctyl-1,3-
Dioxolan and the like. As cyclic acid anhydrides, phthalic anhydride, maleic anhydride, succinic anhydride, etc., and as lactams, β-propiolactam, γ-
Butyrolactam, δ-caprolactam and the like. Examples of the aryl dialdehydes include 1,2-benzenedicarboxaldehyde, 1,2-naphthalenedialdehyde, and the like.

These may be used alone or in combination of two or more.

The photosensitizer [A] is used in an amount of preferably 0.01 to 10 parts by weight, and more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the photocationic polymerizable compound. Is desirable. When the amount of the photosensitizer is less than 0.01 part by weight, the curability is lowered. On the other hand, when the amount is more than 10 parts by weight, the cost is increased and the coating properties such as water resistance are undesirably reduced.

The cationic photopolymerizable agent [B] is used in an amount of preferably 0.01 to 20 parts by weight, and more preferably 0.1 to 1 part by weight, per 100 parts by weight of these cationic photopolymerizable compounds.
A range of 0 parts by weight is desirable. When the amount of the cationic photopolymerization initiator is less than 0.01 part by weight, the curability is reduced.
Exceeding the weight part is not preferable because the price becomes high and the coating performance such as water resistance is deteriorated.

The curable composition of the present invention may optionally contain an ultraviolet absorber. The ultraviolet absorber is a substance that absorbs ultraviolet light of 400 nm or less.
As this, for example, benzotriazole type and benzophenone type are particularly preferable. Specifically, Tinuvin 144, Tinuvin 292, Tinuvin 327, Tinuvin 7
70, Tinuvin 900 (Ciba Specialty Chemicals), Siasorb UV531 (American Cya
namid Corp.). In addition, cerium salts and titanium dioxides can also be used.

The curable composition of the present invention may contain, if necessary, other resins, fillers, colorants, pigments, pigment dispersants, flow regulators, leveling agents, defoamers, light stabilizers, antioxidants. An agent, a gel particle, a fine particle powder and the like may be blended.

The curable composition of the present invention can be applied to base materials such as films of metals, cans, plastics, papers, wood materials, inorganic materials, PET and the like, and combinations thereof.

In the method for forming a coating film of the present invention, the above active energy ray-curable composition is applied to the surface of the above-mentioned base material so that the applied amount is 1 to 100 μm in the cured film thickness. For curing.

The active energy ray referred to in the present invention is, for example, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, an incandescent lamp, a xenon lamp, a carbon arc lamp, a metal halide lamp, a fluorescent lamp, a tungsten lamp, a gallium lamp. , Excimer, laser, electron beam, γ-ray and the like can be used.

[0080]

EXAMPLES Examples will be described in more detail.

Example 1 1 part of 9,10-diethoxyanthracene, 1 part of bis (4-tert-butylphenyl) iodonium hexafluorophosphate (BBI-102, manufactured by Midori Kagaku Co.), 3,4-epoxycyclohexyl Methyl-
100 parts of 3,4-epoxycyclohexanecarboxylate (manufactured by Union Carbide Co., Ltd., UVR-6110) was added and mixed to obtain an active energy ray-curable composition (I).

This composition was applied on a tin plate and subjected to spectral irradiation. Spectral irradiator CR, manufactured by JASCO Corporation
The curing range of this composition was examined by irradiating light of 200 nm to 700 nm using M-FA. As a result, spectral sensitivity was obtained from 205 nm to 450 nm.

In the case where 9,10-diethoxyanthracene was not added, the spectral sensitivity was 230 nm to 310 nm.

The composition was applied to a glass plate and irradiated with a metal halide lamp at 200 mJ / cm ² . The obtained coating film had a gel fraction of 87% and a pencil hardness of 3-4H, which was good.

Comparative Example 1 A composition of Comparative Example 1 was obtained in the same manner as in Example 1 except that 9,10-diethoxyanthracene was not added. This had a spectral sensitivity of 230 nm to 310 nm. The obtained coating film was inferior at a gel fraction of 78% and a pencil hardness of 2 to 4H.

Example 2 Epoxy-containing acrylic copolymer (styrene / methyl methacrylate / glycidyl methacrylate / hydroxyethyl methacrylate = 15/19/50/16, number average molecular weight 4,000, epoxy having a molecular weight of 3.52 per 1,000) 20 parts, bis- (3,4-epoxycyclohexyl) adipate (product of Union Carbide, U.S.A.)
VR-6128), 20 parts, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (Celloxite 202, manufactured by Daicel Chemical Industries, Ltd.)
1P) 40 parts, limonenedioxide 20 parts, 2-ethyl-9,10-dimethoxyanthracene 0.7 part as photosensitizer, UVI-699 as photocationic polymerization initiator
0 (manufactured by Union Carbide Co., Ltd., triarylsulfonium hexafluorophosphate salt) (5 parts) and titanium dioxide (40 parts) were added and mixed to obtain a white enamel paint (II).

This paint was applied to an aluminum plate with a bar coater so as to have a thickness of 10 μm and subjected to spectral irradiation. Spectral sensitivity was obtained from 230 nm to 495 nm.

This white paint composition was coated on polyethylene-terephthalate (PE) on ten-free steel (TFS).
T) 8 μm thick on the substrate on which the film was laminated
Was applied with a roll coater and irradiated with a metal halide lamp at 250 mJ / cm ² to cure the coating.

The obtained coating film had a pencil hardness of 2H and a gel fraction of 85%, which was good.

Comparative Example 2 A composition of Comparative Example 2 was obtained in the same manner as in Example 2 except that 2-ethyl-9,10-dimethoxyanthracene was not added. This is 230nm ~ 3
The spectral sensitivity was 70 nm. Gel fraction 4 of the obtained coating film
2%, and the pencil hardness was inferior at 6B or less.

Example 3 1.5 parts of photosensitizer 9,10-diethoxyanthracene
P, P'-bis ((triphenylphosphonino) methyl) benzophenone hexafluoroantimonate 3
Part, 3,4-epoxycyclohexylmethyl-3,4-
Epoxycyclohexanecarboxylate 60 parts, TONE
Polyol 0301 (product of Union Carbide, ε-caprolactone triol, OH value 100), 10 parts, acrylic copolymer (styrene / methyl methacrylate / n-butyl methacrylate / 2-ethylhexyl methacrylate / 3 / methacryloxymethyl-3-ethyloxetane) =
20/10/15/15/40, number average molecular weight 4,20
0, containing 2.3 oxetane rings per 1,000 molecular weight)
10 parts, 10 parts of β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and 20 parts of titanium dioxide were added, mixed and dispersed to obtain a white enamel paint.

This white enamel paint was applied to an aluminum plate so as to have a thickness of 6 μm, and curability was examined by spectrally irradiating light having a wavelength of 200 nm to 700 nm.

As a result, the coating film was cured in the range from 210 nm to 470 nm.

This white enamel paint was applied to a polycarbonate plate so as to have a thickness of 20 μm, and irradiated with a metal halide lamp at 400 mJ / cm ² . The pencil hardness of the obtained coating film was 4H.

Comparative Example 3 A composition of Comparative Example 3 was obtained in the same manner as in Example 3 except that 9,10-diethoxyanthracene was not added. This had a spectral sensitivity of 210 nm to 360 nm. The resulting coating film had a gel fraction of 55% and a pencil hardness of 3B, which was inferior.

Example 4 1.5 parts of 9,10-butoxyanthracene, 80 parts of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 20 parts of diethylene glycol divinyl ether, PI-2855 (manufactured by Nippon Soda Co., Ltd.) , A sulfonium salt-based photocationic polymerization initiator) 5 parts,
50 parts of titanium dioxide was added, mixed and dispersed to obtain a white enamel paint (III).

This white enamel paint (III) was applied to a tin plate and irradiated with light having a wavelength of 200 nm to 700 nm spectrally.

Curing of the coating occurred in the range of light wavelengths from 210 nm to 510 nm.

This white enamel paint (III) was applied to a glass plate by a roll coater so as to have a thickness of 15 μm, and irradiated with a gallium lamp at 300 mJ / cm ² to cure the coating.
The pencil hardness was 4H and the gel fraction was 90%.

Comparative Example 4 A composition of Comparative Example 4 was obtained in the same manner as in Example 4 except that 9,10-butoxyanthracene was not added. This had a spectral sensitivity of 230 nm to 340 nm. The obtained coating film was inferior in gel fraction of 30% and pencil hardness of 6B or less.

Example 5 2 parts of 2-ethyl-9,10-diethoxyanthracene
Acrylic copolymer (glycidyl methacrylate / 3-methacryloxymethyl-3-ethyloxetane / styrene / n-butyl methacrylate = 30/30/27/1
3, number average molecular weight 4,000, glass transition temperature 68 ° C)
20 parts, γ-glycidoxypropyltrimethoxysilane 20 parts, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane 20 parts, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate 30 parts , 10 parts of xylylene dioxetane,
4 parts of DAICAT-11 (manufactured by Daicel Chemical Industries, Ltd., sulfonium salt-based cationic photopolymerization initiator) was added, mixed and dissolved to obtain an active energy ray-curable composition (V).

The coating composition (V) was applied to an aluminum plate, and the coating was cured by spectrally irradiating light of 200 nm to 700 nm.

This coating material was cured in the range of 200 nm to 530 nm.

The paint (V) was applied to an aluminum plate to a thickness of 1
Paint to 0μm, with metal halide lamp,
Irradiation was performed at 120 mJ / cm ² . The pencil hardness of the obtained coating film is 4H
Met.

Comparative Example 5 A composition of Comparative Example 5 was obtained in the same manner as in Example 5, except that 2-ethyl-9,10-diethoxyanthracene was not added. This is 210nm ~ 4
The spectral sensitivity was 00 nm. Gel fraction of the obtained coating film 7
The pencil hardness was inferior to H at 2%.

Example 6 50 parts of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 20 parts of xylylenedioxetane, acrylic copolymer (3-methacryloxymethyl-3-ethyloxetane / 3- Acryloxymethyl-3-ethyloxetane / 3,4-epoxycyclohexylmethyl methacrylate / styrene / methyl methacrylate = 10/20/30/20/20;
(Number average molecular weight 4,000, Tg: 70 ° C.) 15 parts, limonenedioxide 15 parts, photosensitizer 2-methyl-9,1
1 part of 0-diethoxyanthracene, 5 parts of cationic photopolymerization initiator DAICAT-11 (manufactured by Daicel Chemical Industries, Ltd., sulfonium-based cationic photopolymerization initiator), 5 parts of titanium dioxide
0 parts and 2 parts of an ultraviolet absorber tinuvin were added and mixed to obtain a white enamel paint (VI).

The white enamel paint (VI) was applied to a tin plate and subjected to spectral irradiation from 200 nm to 700 nm. 3
Curing of the coating was obtained at wavelengths from 50 nm to 550 nm.

This white enamel paint (VI) was applied to an ABS resin so as to have a thickness of 25 μm, and irradiated with an incandescent lamp for 2 minutes. The pencil hardness of the obtained coating film is 3H, and the gel fraction is 98%.
Met.

Comparative Example 6 A composition of Comparative Example 6 was obtained in the same manner as in Example 6, except that 2-methyl-9,10-diethoxyanthracene was not added. This is 360nm ~ 4
The spectral sensitivity was 00 nm. This coating film was irradiated with a tungsten lamp for 10 minutes, but was not cured and was inferior.

Example 7 85 parts of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 10 parts of xylylenedioxetane, 5 parts of TONE Polyol 0301, 9,
2 parts of 10-diethoxyanthracene, titanium dioxide 30
Part and 0.5 part of phthalocyanine mumble were mixed and dispersed to obtain a light blue paint.

To 100 parts of the paint, UVR-6110 was added.
(Photocationic polymerization initiator manufactured by Union Carbide) 2
The parts were mixed and dispersed to obtain paint (VII).

The paint (VII) was applied to a tin plate,
Spectral irradiation was performed from 0 nm to 700 nm. 250nm-5
Curing of the coating was observed at light wavelengths up to 30 nm.

The coating material was applied to a coated paper so as to have a thickness of 10 μm, and irradiated with a metal halide lamp at 300 mJ / cm ² . The obtained coating film had good appearance and adhesion.

Comparative Example 7 A composition of Comparative Example 7 was obtained in the same manner as in Example 7 except that 9,10-diethoxyanthracene was not added. This had a spectral sensitivity of 360 nm to 400 nm. The resulting coating film had insufficient curing of the lower part.

Example 8 2-Ethyl-9,10-dimethoxyanthracene (2 parts)
CI-2855 (Nippon Soda Co., Ltd., sulfonium-based cationic photopolymerization initiator) 5 parts, celloxite 2021P (Daicel Chemical Industries, Ltd., alicyclic epoxy compound) 100 parts,
50 parts of titanium dioxide, UV absorber Iasium UV-
531 (American Cyanamid Corp.) was added, mixed and dispersed by a dispersion to obtain a white enamel paint (VIII).

This white enamel paint (VIII) was applied to a primer-coated aluminum plate,
Spectroscopic irradiation of light was performed. Spectral sensitivities from 300 nm to 500 nm were obtained.

This white enamel paint was applied to a polycarbonate plate so as to have a thickness of 15 μm, and the paint was cured by irradiating the paint with a gallium metal halide lamp at 400 mJ / cm ² . The resulting coating film had a good finish and good adhesion.

Comparative Example 8 A composition of Comparative Example 8 was obtained in the same manner as in Example 8, except that 9,10-diethoxyanthracene was not added. This obtained spectral sensitivity only up to 250 nm to 300 nm. Further, irradiation with light was performed in the same manner as in Example 8, but the coating was not cured.

Example 9 Acrylic copolymer (styrene / methyl methacrylate /
n-butyl methacrylate / 2-ethylhexyl methacrylate / 3 / methacryloxymethyl-3-ethyloxetane = 20/10/15/15/40, number average molecular weight 4,200, oxetane ring 2.3 per 1,000 molecular weight
10 parts), 20 parts of 3-ethyl-3-hydroxymethyloxetane, 70 parts of the above celoxide 2021P.
Part, 2-methyl-9,10-diethoxyanthracene 3
And 30 parts of titanium dioxide were mixed and dispersed to obtain a white enamel. Then, the above DACA was added to 100 parts of the obtained white enamel.
Five parts of T-11 were added to obtain a white enamel paint (IX).

After the base material was coated with a urethane primer and dried, the surface of the coating film was sanded, a white enamel paint (IX) was applied to a thickness of 40 μm, and irradiated with a tungsten lamp for 4 minutes. The resulting coating film had a pencil hardness of 3H and a good finished appearance.

Comparative Example 9 A composition of Comparative Example 9 was obtained in the same manner as in Example 9 except that 2-methyl-9,10-diethoxyanthracene was not added. Irradiation was carried out in the same manner as in Example 9, but the coating was not cured.

Example 10 Acrylic copolymer (glycidyl methacrylate / 3-methacryloxymethyl-3-ethyloxetane / styrene / n-butyl methacrylate = 30/30/27/1
3, number average molecular weight 4,000, glass transition temperature 68 ° C)
15 parts, 3-ethyl-3- (glycidyloxymethyl)
15 parts of oxetane, 60 parts of celoxite 2021P
, 10 parts of limonenedioxide, 3 parts of 9,10-diethoxyanthracene, 10 parts of calcium carbonate and 10 parts of titanium dioxide were mixed and dispersed to obtain a white enamel. Next, 100 parts of the obtained white enamel was mixed with 3 parts of DACCAT-11.
To obtain a white enamel paint (X).

After coating and drying a melamine-curable acrylic resin primer on the substrate, sanding the coating film surface, applying a white enamel paint (X) to a film thickness of 60 μm, and using a tungsten lamp for 3 minutes Irradiated. The resulting coating film had a pencil hardness of 3H and a good finished appearance.

Comparative Example 10 A composition of Comparative Example 10 was obtained in the same manner as in Example 10, except that 9,10-diethoxyanthracene was not added. Irradiation was carried out in the same manner as in Example 10, but the coating was not cured.

[0125]

The composition of the present invention is a composition obtained by blending a specific photosensitizer with a cationic photopolymerizable composition. Therefore, the composition is excellent in photocurability even in an enamel type containing a pigment. It has a special effect.

Claims (7)

[Claims] 1. The following component [A]: a photosensitizer represented by the following general formula (1): (Wherein, R ₁ and R ₂ are a C ₁ -C ₈ alkyl group, and R ₃ are the same or different and each represent a hydrogen atom or a C ₁ -C ₄ alkyl group.) [B] Iodonium salt, sulfonium salt and A composition comprising, as essential components, at least one type of cationic photopolymerization initiator selected from phosphonium salts and [C] a cationic photopolymerizable compound, wherein the components [A], [B] and [C] The compounding ratio is [A] 0.01 to 100 parts by weight [C].
An active energy ray-curable composition, characterized in that the content is 5 parts by weight and [B] 0.1 to 20 parts by weight. 2. The photocurable composition according to claim 2, wherein the curable composition is a photosensitizer.
The curable composition according to claim 1, wherein [A] is 9,10-dimethoxyanthracene. 3. The photocurable composition according to claim 1, wherein the curable composition is a photosensitizer.
The curable composition according to claim 1, wherein [A] is 9,10-diethoxyanthracene. 4. The photocurable composition according to claim 1, wherein the curable composition is a photosensitizer.
The curable composition according to claim 1, wherein [A] is 2-ethyl-9,10-dimethoxyanthracene. 5. The photocurable composition according to claim 1, wherein the curable composition is a photosensitizer.
The curable composition according to claim 1, wherein [A] is 2-ethyl-9,10-diethoxyanthracene. 6. The curable composition according to claim 1, further comprising an ultraviolet absorbent [D].
The curable composition according to any one of the above. 7. An active energy ray-curable composition according to any one of claims 1 to 6, which is applied to a surface of a base material so that a coating amount is 1 to 100 microns in a cured film thickness. A method for forming a coating film, comprising irradiating with an active energy ray to cure the film.